The present invention relates to a hot-melt silicone adhesive composition and more particularly to a hot-melt silicone adhesive composition containing an electrically conductive filler and a hydroxy-functional organic compound.
Hot-melt silicone adhesives are useful in a variety of applications because they possess the processing advantages of hot-melt adhesives in combination with the performance advantages of silicones, such as thermal stability, good moisture resistance, excellent flexibility, high ionic purity, low alpha particle emissions, and good adhesion to various substrates. For example, hot-melt silicone adhesives are potentially useful in the medical, automotive, electronic, construction, appliance, and aerospace industries.
Hot-melt silicone pressure sensitive adhesive (PSA) compositions are known in the art. For example, hot-melt silicone PSA compositions comprising a silicone fluid and a silicone resin are disclosed in U.S. Pat. Nos. 5,371,128; 4,865,920; 5,328,696; 5,658,975; 5,578,319; 5,147,916; 5,246,997; 5,290,564; 5,162,410; 5,482,988; 5,352,722; and 5,300,299. Moreover, moisture-curable hot-melt silicone PSA compositions are disclosed in U.S. Pat. Nos. 5,508,360; 5,340,887; 5,473,026; 5,302,671; and 5,905,123. However, the preceding references do not teach the electrically conductive filler and the hydroxy-functional organic compound of the present invention.
Hot-melt adhesive compositions comprising a thermoplastic silicone block copolymer and an electrically conductive filler are also known in the art. For example, U.S. Pat. No. 4,820,446 to Prud""Home discloses an electrically conductive, potentially adhesive composition comprising a thermoplasitc block copolymer containing polysiloxane and urethane groups having elastomeric properties, and particles whose surface at least is electrically conductive. Furthermore, U.S. Pat. No. 4,822,523 to Prud""Home discloses an electrically conductive, potentially adhesive composition comprising a thermoplastic polyblock organopolysiloxane copolymer having elastomeric properties, and particles whose surface at least is electrically conductive. However, neither of the aforementioned patents teaches the hydroxy-functional organic compound of the present invention.
The present invention is directed to an electrically conductive hot-melt silicone adhesive composition, comprising:
(A) a hot-melt silicone adhesive;
(B) an electrically conductive filler in an amount sufficient to impart electrical conductivity to the composition, wherein the filler comprises particles having at least an outer surface of a metal selected from silver, gold, platinum, palladium, and alloys thereof; and
(C) an effective amount of a hydroxy-functional organic compound having a molecular weight up to about 1000 and containing at least one hydroxy group per molecule, provided that when the composition is curable, the compound does not substantially inhibit cure.
The silicone composition of this invention has numerous advantages, including good flow, low VOC (volatile organic compound) content, good adhesion, and unexpectedly superior electrical conductivity as evidenced by low contact resistance and/or volume resistivity.
The silicone composition of this invention has numerous uses, including die attach adhesives, solder replacements, and electrically conductive coatings and gaskets. In particular, the silicone composition is useful for bonding electronic components to flexible or rigid substrates. The composition of the present invention is also useful as a thermal interface material in semiconductor packages. For example, the silicone composition can be used as the thermal interface between heat-generating semiconductor elements, such as power transistors and integrated circuits, and substrates, lead frames, and heat-dissipating fins.
These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.
This invention pertains to an electrically conductive hot-melt silicone adhesive composition, comprising:
(A) a hot-melt silicone adhesive;
(B) an electrically conductive filler in an amount sufficient to impart electrical conductivity to the composition, wherein the filler comprises particles having at least an outer surface of a metal selected from silver, gold, platinum, palladium, and alloys thereof; and
(C) an effective amount of a hydroxy-functional organic compound having a molecular weight up to about 1000 and containing at least one hydroxy group per molecule, provided that when the organosilicon composition is curable, the compound does not substantially inhibit cure.
Component (A) of this invention is at least one hot-melt silicone adhesive. As used herein, the term xe2x80x9chot-meltxe2x80x9d describes a silicone adhesive that is nonflowable at room temperature, but converts to a flowable state at an elevated temperature, for example, from about 50 to about 200xc2x0 C. Component (A) can be any hot-melt silicone adhesive known in the art, provided the silicone composition formed by combining component (A) with components (B) and (C) exhibits improved contact resistance and/or volume resistivity compared with a similar silicone composition lacking only the hydroxy-functional organic compound. The hot-melt silicone adhesive can be a noncurable adhesive that becomes flowable at an elevated temperature and reverts to a nonflowable state upon cooling. Alternatively, the hot-melt silicone adhesive can be a curable adhesive that undergoes a curing (crosslinking) reaction after the adhesive has been applied to a substrate. Component (A) can be a single hot-melt silicone adhesive or a mixture comprising two or more different hot-melt silicone adhesives.
Hot-melt silicone adhesives suitable for use in the silicone composition of this invention include, but are not limited to, hot-melt silicone pressure sensitive adhesives comprising a silicone fluid and an organopolysiloxane resin; thermoplastic silicone-organic block copolymers; and moisture-curable hot-melt silicone pressure sensitive adhesives. Examples of the aforementioned hot-melt silicone adhesives and methods for their preparation are well known in the art. The U.S. patents cited in the Background section are hereby incorporated by reference to teach hot-melt silicone adhesives suitable for use in the silicone composition of the present invention.
Component (B) of this invention is at least one electrically conductive filler comprising particles having at least an outer surface of a metal selected from silver, gold, platinum, palladium, and alloys thereof. Fillers comprising particles consisting of a metal selected from silver, gold, platinum, palladium, and alloys thereof typically have the form of a powder or flakes with an average particle size of from 0.5 to 20 xcexcm. Fillers comprising particles having only an outer surface of a metal selected from silver, gold, platinum, palladium, and alloys thereof typically have an average particle size of from 15 to 100 xcexcm. The core of the particles can be any electrically conductive or insulative material that supports a surface consisting of the aforementioned metal and does not adversely affect the electrical properties of the silicone composition. Examples of such materials include, but are not limited to, copper, solid glass, hollow glass, mica, nickel, and ceramic fiber.
In the case of electrically conductive fillers comprising metal particles having the form of flakes, the surface of the particles may be coated with a lubricant, such as a fatty acid or fatty acid ester. Such lubricants are typically introduced during the milling process used to produce flakes from a metal powder to prevent the powder from cold welding or forming large aggregates. Even when the flakes are washed with a solvent after milling, some lubricant may remain chemisorbed on the surface of the metal.
The electrically conductive filler of this invention also includes fillers prepared by treating the surfaces of the aforementioned particles with at least one organosilicon compound. Suitable organosilicon compounds include those typically used to treat silica fillers, such as organochlorosilanes, organosiloxane, organodisilazanes, and organoalkoxysilanes.
Component (B) can be a single electrically conductive filler as described above or a mixture of two or more such fillers that differ in at least one of the following properties: composition, surface area, surface treatment, particle size, and particle shape.
Preferably, the electrically conductive filler of the present invention comprises particles consisting of a metal selected from silver, gold, platinum, palladium, and alloys thereof. These solid metal fillers impart thermal conductivity to the composition as well as electrical conductivity. More preferably, the electrically conductive filler comprises particles consisting of silver.
The concentration of component (B) in the silicone composition of this invention is sufficient to impart electrical conductivity to the composition. Typically, the concentration of component (B) is such that the silicone composition has a contact resistance less than about 1xcexa9 and a volume resistivity less than about 0.01 xcexa9xc2x7cm, as determined using the methods in the Examples below. The exact concentration of component (B) depends on the desired electrical properties, surface area of the filler, density of the filler, shape of the filler particles, surface treatment of the filler, and nature of the other components in the silicone composition. The concentration of component (B) is typically from about 15 to about 80 percent by volume and preferably from about 20 to about 50 percent by volume, based on the total volume of the electrically conductive hot-melt silicone adhesive composition. When the concentration of component (B) is less than about 15 percent by volume, the silicone composition typically does not have significant electrical conductivity. When the concentration of component (B) is greater than about 80 percent by volume, the silicone composition typically does not exhibit further substantial improvement in electrical conductivity.
Methods of preparing electrically conductive fillers are well known in the art; many of these fillers are commercially available. For example, powders of silver, gold, platinum, or palladium, or alloys thereof are typically produced by chemical precipitation, electrolytic deposition, or atomization. Also, flakes of the aforementioned metals are typically produced by grinding or milling the metal powder in the presence of a lubricant, such as a fatty acid or fatty acid ester. Particles having only an outer surface of at least one of the aforementioned metals are typically produced by metallizing an appropriate core material using a method such as electrolytic deposition, electroless deposition, or vacuum deposition.
The electrically conductive filler of this invention can be a filler prepared by treating the surfaces of the aforementioned particles with at least one organosilicon compound. In this case, the particles can be treated prior to admixture with the other ingredients of the silicone composition or the particles can be treated in situ during the preparation of the silicone composition.
Component (C) of this invention is at least one hydroxy-functional organic compound having a molecular weight up to about 1000 and containing at least one hydroxy group per molecule, provided that when the composition is curable, the compound does not substantially inhibit cure. When the molecular weight of the hydroxy-functional organic compound is greater than about 1000, the silicone composition does not have substantially improved electrical conductivity relative to a similar silicone composition lacking only the hydroxy-functional organic compound. As used herein, the term xe2x80x9csubstantially inhibit curexe2x80x9d means to prevent cure or retard cure to the point where the cure rate is impracticably slow, for example, several weeks at room temperature or several days at about 150xc2x0 C. Preferably, the silicone composition of the present invention cures in less than about 7 days at 25xc2x0 C.
The structure of the hydroxy-functional organic compound can be linear, branched, or cyclic. The hydroxy group(s) in the hydroxy-functional organic compound may be attached to a primary, secondary or tertiary aliphatic carbon atom; an aromatic carbon atom; or a doubly bonded carbon atom in the molecule. Furthermore, there are no restrictions on the stereochemistry of the hydroxy-bearing carbon atom(s) or the molecule.
The hydroxy-functional organic compound can contain one or more functional groups other than hydroxy, provided that when the organosilicon composition is curable, the compound does not substantially inhibit cure of the composition. Examples of suitable functional groups include, but are not limited to, xe2x80x94Oxe2x80x94,  greater than Cxe2x95x90O, xe2x80x94CHO, xe2x80x94CO2xe2x80x94,xe2x80x94Cxe2x89xa1N, xe2x80x94NO2,  greater than Cxe2x95x90C less than , xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94F, xe2x80x94Cl, xe2x80x94Br, and xe2x80x94I. However, hydroxy-functional organic compounds containing functional groups that strongly complex the metal in a condensation catalyst may substantially inhibit cure of the organosilicon composition. For example, when a tin catalyst is used, hydroxy-functional organic compounds containing thiol (-SH) groups are generally avoided. The degree of inhibition depends on the particular combination of functional group and metal and the mole ratio thereof. The suitability of a particular hydroxy-functional organic compound for use in the silicone composition of the present invention can be readily determined by routine experimentation using the methods in the Examples below.
The hydroxy-functional organic compound can be a naturally occurring or synthetic compound having a liquid or solid state at room temperature. Also, the hydroxy-functional organic compound can be soluble, partially soluble, or insoluble in the silicone composition. The normal boiling point of the hydroxy-functional organic compound, which depends on the molecular weight, structure, and number and nature of functional groups in the compound, can vary over a wide range. Preferably, the hydroxy-functional organic compound has a normal boiling point greater than the temperature at which the silicone composition becomes flowable. Otherwise, appreciable amounts of the hydroxy-functional organic compound may be removed by volatilization during heating, resulting in little or no enhancement in the conductivity of the silicone composition. Also, excessive volatilization of the hydroxy-functional organic compound during heating may cause formation of voids in the silicone composition.
Examples of hydroxy-functional compounds suitable for use in the silicone composition of the present invention include, but are not limited to, monohydric alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, hepatanol, nonanol, decanol, undecanol, 1-phenylethanol, benzyl alcohol, allyl alcohol, 3-nitrobenzyl alcohol, 3-chlorobenzyl alcohol, 3-bromobenzyl alcohol, 3-iodobenzyl alcohol, and diethylene glycol butyl ether; dihydric alcohols such as ethylene glycol, propylene glycol (1,2-propanediol), polyethylene glycol, polypropylene glycol, polytetrahydrofuran, benzopinacole, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, trimethylene glycol (1,3-propanediol), 1,5-pentanediol, 1,6-hexanediol, and bis(2-hydroxyethyl)ether; polyhydric alcohols such as glycerol, pentaerythritol, dipentaerythritiol, tripentaerythritol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, 1,3-dihydroxyacetone dimer, sorbitol, and mannitol; phenols such as phenol, 1-hydroxynaphthalene, 1,2-dihydroxynaphthalene, hydroquinone, catechol, resorcinol, phloroglucinol (1,3,5-trihydroxybenzene), p-cresol, vitamin E, 2-nitrophenol, 2,4-dinitrophenol, picric acid (2,4,6-trinitrophenol), 4-chlorophenol, 2-bromophenol, 2-iodophenol, 2,4,5-tricholorophenol, chlorohydroquinone, pentachlorophenol; sugars such as glucose, mannose, allose, altrose, idose, gulose, galactose, talose, ribose, arabinose, xylose, lyxose, erythrose, threose, glyceraldehyde, fructose, ribulose, lactose, maltose, and sucrose; hydroxy aldehydes such as 2-hydroxybutyraldehyde, 4-hydroxybenzaldehyde, and 2,4-dihydroxybenzaldehyde; hydroxy ketones such as hydroxyacetone, 1-hydroxy-2-butanone, 2xe2x80x2, 4xe2x80x2-dihydroxyacetophenone, benzoin, and 3-hydroxy-2-butanone; hydroxy acids such as citric acid, gluconic acid, 3-hydroxybutyric acid, 2-hydroxycinnamic acid, and salicylic acid (2-hydroxybenzoic acid); and hydroxy esters such as ascorbic acid, TWEEN 20 (polyoxyethylene (20) sorbitan monolaurate), methyl salicylate, methyl 3-hydroxybenzoate, and methyl 2-hydroxyisobutyrate.
Component (C) is present in an effective amount in the silicone composition of this invention. As used herein, the term xe2x80x9ceffective amountxe2x80x9d means that the concentration of component (C) is such that the silicone composition has improved electrical conductivity, initial contact resistance and/or volume resistivity, compared with a similar silicone composition lacking only the hydroxy-functional organic compound. Typically, the concentration of component (C) is such that the silicone composition exhibits at least about a two-fold improvement in either contact resistance or volume resistivity, as determined using the methods in the Examples below. The concentration of component (C) is typically from about 0.1 to about 3 percent by weight and preferably from about 0.5 to about 1.5 percent by weight, based on the total weight of the silicone composition. When the concentration of component (C) is less than about 0.1 percent by weight, the silicone composition typically does not exhibit improved electrical conductivity. When the concentration of component (C) is greater than about 3 percent by weight, the silicone composition typically does not exhibit further substantial improvement in electrical conductivity. The effective amount of component (C) can be determined by routine experimentation using the methods in the Examples below.
Methods of preparing hydroxy-functional organic compounds suitable for use in the silicone composition of the present invention are well known in the art; many of these compounds are commercially available.
The silicone composition of the present invention can further comprise at least one adhesion promoter. The adhesion promoter can be any adhesion promoter typically employed in uncured and condensation-curable silicone compositions, provided it does not adversely affect the physical properties of the silicone composition, particularly contact resistance and volume resistivity.
Examples of adhesion promoters suitable for use in the silicone composition of the present invention include, but are not limited to, amino-functional alkoxysilanes such as
H2N(CH2)3Si(OCH3)3, H2N(CH2)3Si(OCH2CH3)3,
H2N(CH2)3Si(OCH2CH2OCH3)3, H2N(CH2)4Si(OCH3)3,
H2NCH2CH(CH3)CH2CH2SiCH3(OCH3)2, H2N(CH2)2NH (CH2)3 Si(OCH3)3,
H2N(CH2)2NH(CH2)3Si(OCH2CH2OCH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH3)3,
H2N(CH2)2NH(CH2)3Si(CHxe2x95x90CH2)(OCH3)2; epoxy-functional alkoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 1,2-epoxy-4-(2-trimethoxysilylethyl)cyclohexane, and 1,2-epoxy-2-methyl-4-(1-methyl-2-trimethoxysilylethyl)cyclohexane; reaction products of at least one amino-functional alkoxysilane and at least one epoxy-functional alkoxysilane such as reaction products of 3-glycidoxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and [3-(2-aminoethyl) aminopropyl]trimethoxysilane, 1,2-epoxy-4-(2-trimethoxysilylethyl) cyclohexane and 3-aminopropyltrimethoxysilane, 1,2-epoxy-4-(2-trimethoxysilylethyl) cyclohexane and [3-(2-aminoethyl)aminopropyl]trimethoxysilane, 1,2-epoxy-2-methyl-4-(1-methyl-2-trimethoxysilylethyl)cyclohexane and 3-aminopropyltrimethoxysilane, and 1,2-epoxy-2-methyl-4-(1-methyl-2-trimethoxysilylethyl)cyclohexane and [3-(2-aminoethyl)aminopropyl]trimethoxysilane; and vinyl trialkoxysilanes such as (CH3O)3SiCHxe2x95x90CH2, (CH3CH2O)3SiCHxe2x95x90CH2, (CH3 CH2CH2O)3SiCHxe2x95x90CH2, (CH3CH2 CH2CH2O)3SiCHxe2x95x90CH2, and (CH3OCH2CH2O)3SiCHxe2x95x90CH2.
The concentration of the adhesion promoter in the silicone composition of this invention is sufficient to effect adhesion of the composition to a substrate, such as those cited above. The concentration can vary over a wide range depending on the nature of the adhesion promoter, the type of substrate, and the desired adhesive bond strength. The concentration of the adhesion promoter is generally from 0.01 to about 10 percent by weight, based on the total weight composition. However, the optimum concentration of the adhesion promoter can be readily determined by routine experimentation.
Methods of preparing amino-functional alkoxysilanes are well known in the art as exemplified in U.S. Pat. No. 3,888,815 to Bessmer et al. Methods of preparing epoxy-functional alkoxysilanes, such as the hydrosilylation addition reaction of alkenyl-containing epoxysilanes with trialkoxysilanes, and methods of preparing vinyl trialkoxysilanes, such as the reaction of vinyltrichlorosilane with alcohols, are also well known in the art. Reaction products of amino-functional alkoxysilanes and epoxy-functional alkoxysilanes can be prepared using well known methods of reacting epoxy-containing compounds with amines. The reaction is typically carried out using about a 1:1 mole ratio of epoxy groups in the epoxy-functional alkoxysilane to nitrogen-bonded hydrogen atoms in the amino-functional alkoxysilane. The two compounds can be reacted either in the presence of an inert organic solvent, such as toluene, or in the absence of a diluent. The reaction can be carried out at room temperature or an elevated temperature, for example, from about 50 to about 100xc2x0 C.
The silicone composition of the instant invention is typically prepared by mixing components (A) through (C) and any optional ingredients in the stated proportions at ambient temperature with or without the aid of an organic solvent. Mixing can be accomplished by any of the techniques known in the art such as milling, blending, and stirring, either in a batch or continuous process. Examples of suitable organic solvents include hydrocarbons, such as xylene, toluene, and heptane. The organic solvent can be removed to provide an essentially solvent-free silicone composition by heating the mixture under reduced pressure.
The silicone composition can be applied to a wide variety of solid substrates including, but not limited to, metals such as aluminum, gold, silver, tin-lead, nickel, copper, and iron, and their alloys; silicon; fluorocarbon polymers such as polytetrafluoroethylene and polyvinylfluoride; polyamides such as Nylon; polyimides; polyesters; ceramics; and glass. Typically, the silicone composition is heated to a temperature sufficient to induce flow, for example, from about 50 to about 200xc2x0 C., before application to a substrate. However, the silicone composition can also be applied to a substrate in an organic solvent. The silicone composition can be applied to various substrates using equipment conventionally employed for dispensing organic hot-melt adhesives, such as hot-melt guns, sprayers, extruders, heated draw-down bars, doctor blades, and calandar rolls.
The silicone composition has numerous advantages, including good flow, low VOC (volatile organic compound) content, good adhesion, and unexpectedly superior electrical properties.
With regard to flow, the silicone composition becomes flowable at an elevated temperature and reverts to a nonflowable state upon cooling. The flowable liquid possess the rheological properties required for a number of applications and is easily dispensed and applied using standard equipment.
Furthermore, the silicone composition has a very low VOC (volatile organic compound) content. Consequently, the silicone composition avoids the health, safety, and environmental hazards associated with solvent-borne silicone compositions. In addition, the solventless composition of the present invention typically undergoes less shrinkage during curing than solvent-borne silicone compositions.
Further, the silicone composition exhibits good adhesion to a wide variety of materials, including metals, glass, silicon, silicon dioxide, ceramics, polyesters, and polyimides.
Importantly, the silicone composition has unexpectedly improved electrical conductivity, as evidenced by a low initial contact resistance and/or volume resistivity, compared with a similar silicone composition lacking only the hydroxy-functional organic compound.
The silicone composition has numerous uses, including die attach adhesives, solder replacements, and electrically conductive coatings and gaskets. In particular, the silicone composition is useful for bonding electronic components to flexible or rigid substrates. The composition of the present invention is also useful as a thermal interface material in semiconductor packages. For example, the silicone composition can be used as the thermal interface between heat-generating semiconductor elements, such as power transistors and integrated circuits, and substrates, lead frames, and heat-dissipating fins.